Treatment of synthetic naphtha



March 6, 1951 B. N. HlLL ET AL 2,544,317

TREATMENT OF SYNTHETIC NAPHTHA Filed Nov. 28, 1947 LIGHT FRACTION BOILING UP TO IIOF.

FRACTION BOILING BETWEEN IIOAND 400F.

' FRACTION BOILING BETWEEN 400AND 600F.

FRAGTIOHATION zone: I8

RAW SYNTHESIS 5 NAPHTHA k r I 2| HEAVY FRACTION AND use!) TREATING MIXTURE 23 TREATING MIXTURE E Patented Mar. 6, 1951 UNITED STATES PATENT- OFFICE TREATMENT OF SYNTHETIC NAIHTHA Boyd N. Hill and Edward'F. Wadley, Baytown, Tex., assign'ors, by' memo assignments; to Standard Oil Development Company, Elizabeth, N. J a. corporation'of Delaware Application November 28, 1947, Serial No. 788,632

1' solaims. (01 2 0-450) The present-invention is directed to'a method I and composition for removing oxygenated organic compounds from hydrocarbons containing them. More particularly, the invention is directed to the treatment of hydrocarbons obtained -by reacting carbon monoxide and hydrogen in the presence of a catalyst.

The pioneering Workby Fischer and Tropsch resulted in a process for producing hydrocarbons and oxygenated organic compounds from carbon monoxide and hydrogen by passing a mixture thereof over a suitable catalyst'to cause a reaction between the materials. -As a result of this work commercial processes have been developed 'to pro- ;duce hydrocarbons and oxygenated organic compounds from carbon monoxide and hydrogen. The product from this synthesis reaction is a synthetic crude petroleum, but, unlike natural crude petroleum, it may contain a considerable quantity of oxygenated organic compound such. as ketones, aldehydes organic acids, esters, and

various other oxygenated hydrocarbon derivatives. These oxygenated organic compounds in themselves are valuable materials, but, in combination with hydrocarbons, they are objectioni able since the hydrocarbons are contaminated by th oxygenated organic compounds and, therefore, are unsuitable for use inv the various petroleum conversion processes where catalysts are employed.

The reason that the'synthetic hydrocarbons,

"produced by the reaction of carbon monoxide and hydrogen and contaminated withoxyg'enated organic compounds are unsuitable in catalytic con- Qversion processes is'that the oxygenated organic compounds react with the catalyst usually em- .ployed, such as the Friedel-Crafts type catalyst.

Notonly do the oxygenatedorganic compounds reactwith the catalyst but they enter into'reaction with the hydrocarbons and produce'prodwould be required if the oxygenated organic compounds were absent.

-gel, solvent extraction with aqueous methanol, and variousother solvents, such as sulfur dioxide and the like and mixtures thereof. It has also been suggested to remove a portion of the oxygenated organic compounds by treatment of the naphtha with variou chemical reagents. The

prior art proposals have largely been unsatisfactory in that, While they are effective in removing .aportion'of the'oxygenated organic contaminantsin the naphtha, they are largely ineffective in substantially completely removing the oxygenated organic compounds.

It has now been discovered that the oxygenated 'organic compounds contained in hydrocarbons may be substantially reduced in quantity by distilling the contaminated hydrocarbon containing these materials over a treating reagent comprising a mixture of alkali metal sul ionates, oil, and alkali metal hydroxide. This treatment serves to remove substantially all of the oxygenated organic compounds from the hydrocarbons, and it i particularly effective in removing ketones which usually resist most treating procedures.

It is, therefore; the main object of the present invention to provide a process for removing oxygenated organic compounds from'naphthas containing them by distilling the naphtha in contact with a mixture of alkali metal sulfonates, oil, and

fjalkali metalhydroxide.

Another objectof the present invention is to ucts of less attractive nature than the product resulting from the catalytic conversion of the hydrocarbon themselves. For example, polymers having lubricating oil qualities may be produced by polymerizing alpha olefin iin the presence of aluminum chloride, but,if these alpha olefins are contaminated with oxygenated organic compounds, as when produced .from'carbon monoxide and hydrogemthe product'is not satisfactory'in that the lubricating oil qualitiesare depreciated Y by the presence of the'oxygenated organic comprovide a method for treating hydrocarbons containing oxygenated organic compounds as contaminants' and olefins whereby the content of oxygenated organic compounds is substantially reduced and the hydrocarbons including the olefins-are made suitable for employment in catalytic conversion operations.

A iurther object of the present invention is to disclose a process whereby a hydrocarbon mixture containing thevarious olefins and oxygenated orpounds. Furthermore, the, oxygenatedorganic compounds react with the catalyst and destroy its activity requiring considerably larger quantities ganic compounds including ketones is treated such that the content of oxygenated organic compounds including'ketones is substantially reduced 1 and 'theolefin made suitable as a feed for produe ing synthetic lubricant polymers. of catalysts to causethe reaction to proceed than Still another object of the present invention is the alkali metal hydroxide in an amount in the range between 10% and Such a mixture is readily formed by sulfonation of a solvent extract, such as a phenol extract, with strong sulfuric acid, followed by neutralization of the oily layer with sodium hydroxide. A base treating mixture which has given good results, after addition of sodium hydroxide, comprises about 90% unsulfonated phenol extract and about 10% sodium sulfonates.

The invention will now be illustrated by referv ence to the drawing in which the sole figure predistillation operation in the presenceofa treat ing mixture including oil, anv alkali metal sul fonate, and an alkali metal hydroxide under conditions to cause substantial removal of oxygensents a flow sheet of a preferred mode of practicing the invention. H Referring now to the drawing, numeral II designates a charge tank containing a hydrocarated organic compounds and-to segregate frac tions boiling in the gasoline and higher boiling ranges which are suitable for catalytic conversion operations. I

The treating mixture employed in the present invention will usually comprise an oilbo'ilin'g 'in the lubricating oilbo'iling range, an alkali metal s'ulfon'ate such as a sodium sulfonate produced by sulfonation of a solvent extract of a lubricating oil fraction and subsequent neutralization thereof, and an alkali metal hydroxide such as sodium hydroxide.

The alkali metal hydroxide is preferably sodium hydroxide, but potassium an'd'lithium hydroxides may be substituted therefor. V

The alkali metal sulfonate is preferably sodium sulfonates, but, like the a.kali metal hydroxide, may be potassium sulfon'ate or lithium sulfonate and under some conditions ammonium sulfonates may be satisfactory.

The oil forming a portion of the treating mixture is preferably an oil boiling in the lubricating oil boiling range and may be a solvent extract of a lubricating oil fraction.

The sulfonates, as mentioned before, may be formed by sulfonation and subsequent neutralization of a solvent extract of 'a lubricating oil fraction, but may also be formed by s'ulfo'nation and subsequent neutralization of alkyl aromatics,

which, in turn, maybe produced by alkylatlon'of aromatic hydrocarbons such as toluene and benzene with high molecular weight olefins having more than five carbon atoms in the 'side chain.

A satisfactory treating reagent may be obtained by treatment of a solvent extract such as a phenol extract of a lubricating oil fraction with strong sulfuric acid to cause sul fonation :of the aromatic constituents contained therein "followed by separation 'of the sludge and neutralization of the oil layer containing sulfonate'd derivatives with sodium hydroxide to form a mixture containing oil, sodium sulfonates, anda small amount of sodium hydroxide. 'To this mixture is added an amount of sodium hydroxide sufiicient to provide an amount of sodium hydroxide between [about 10 to 50 weight per cent of the mixture.

While such a treating reagent maybe -fo'rme'd'by employing an excess of sodium hydroxide in the neutralization, it is to be understood that the treating reagent may be formed by compounding lubricating oil fractions, sodium sulfonates from any source, and sodiumhydroxide.

bon fraction such as a raw synthesis naphtha obtained as the hydrocarbon product from the synthesis of carbon monoxide and hydrogen over an iron catalyst. This fraction is pumped into the system from tank I! by line I2 'and pump I3 which discharges the hydrocarbon feed into a fractionation zone I4. Fractionation zone I4 is The treating reagent, prior-tome"addition of the sodium hydroxide, should contain an amount of oil such as a lubricating oil fraction or a 501- vent extract of a lubricating oil fraction in the range from about to and the alkali metal sulfonate, such as sodium sulfonate, should.

be present in the mixture prior to the addition of provided with a heating means I5 which is illustrated by a coil. This heating means is employed to adjust temperatures and pressures in zone I4. Fractionation zone I4 is shown as'a single distillation tower, but it is understood that it may include a series'of fractional distillation towers. It is also understood that distillation zone I4 will be provided with internal baffling equipment, such as hell cap trays or ether internal equipment, to provide intimate 'eontact between vapors and liquids.

Fractionation zone I4 is also provided "with a line Ifi'to remove light fractions boiling up to about F., line I! by wa'yof which a fraction boiling between 110-and 400 F. may be obtained, line I8 for removal of a fraction boiling between 00 and 600 F., and line 19 controlled by valve tionation zone I4 by line I2 and pump I3 has admixed with it an amount of the treating mixture sufficient-to react with the oxygenated organic compounds contained in the raw synthesis naphtha and to cause removal thereof. Usually raw synthesis naphthas, produced by the reaction of carbon monoxide and hydrogen over an iron catalyst will contain inthe neighborhood of 20 weight per-cen er oxygfe'nated organic compounds. To reac'twith this content of'oxygena'tefd organic compounds, ana fiflll t of treating mixture in the range'rrorii a e-ans toabout ao'vonnne per cent may beemploy'ed. This will depen'don the content of oxygenated organic coiripoun'ds in the raw naphtha and this 'contentwill vary with the catalyst employ'ed'and the conversion conditions under which the naphtha 'is produced. Thle"treatingmixture is 'cdntained'intank 2| and is injected into the system "by line '22 and 23 :which allows the continuous injection 'of the treating mixture. The treating mixturein tank 2| will 'c'o'mprise'a mixture of an'oil such 'as 'ajsolvent extract of 'a lubricating oil, petroleum sodium 'sulfonates, and 'so'diumh'yd'rdxide in the amounts given above.

M The heavy f'ractionsplus used treating mixture, withdrawn from frac't'ior'iaftio'n zone I4 by line I9, may bejrecyc'led in parttmine 2: by branch line 24controlld 'b'y valve 26 and eontaini'ng pump 25. vaivezymayte adjusted to'pr'ov'ide the properraeo of the use'a'trea'tmgmsaure and the fresh treating mixture so tthat the oxy enated organic compounds may be removed from the raw naphtha with greatest efficiency.

The heavy fractions andused treating mixture not recycled in the process may be withdrawn from the system by manipulation of valve 20- in line [9. Thi fraction will contain useful hydrocarbons, Oxygenated organic compounds dissolved in the treating reagent and the used treating reagent. To recover the valuable constituents contained therein, it may be desirable to dilute this fraction after cooling in suitable cooling means, not shown, with water or an aqueous solution to cause the formation of a hydrocarbon I sulfonate to which no sodium hydroxide had been added. In this instance, 10 volumes of the mixture substantially free of sodium hydroxide was employed. Fractionshaving boiling ranges similar to those mentioned above were obtained.

In the fifth and final run on the fifth portion of naphtha, the naphtha was distilled over 33 volume per cent of a solution of 50 B. sodium hydroxide to obtain a single fraction boiling between 110 and 400 F. p

The fractions having the aforementioned boiling ranges were subjected to analysis for oxygenated organic compounds with the results reported in the following table:

layer and the aqueous layer are separable by gravity from each other. The hydrocarbon layer may be further used if desired while a substantial amount of the oxygenated organic compounds containing the aqueous layer may be recovered therefrom by acidification with a mineral acid.

It will be seen from the foregoing description that a simple distillation process including a treating operation has been described wherein a contaminated hydrocarbon containing oxygenated organic compounds is subjected to distillation in the presence of a treating reatgent comprising oil, alkali metal sulfonates, and alkali metal hydroxide to obtain an overhead fraction, substantially free of contaminants, which is useful in catalytic conversion operations.

The invention will now be further illustrated by specific runs in which a naphtha formed by the reaction of carbon monoxide and hydrogen over an iron-type catalyst was divided into five portions. One portion was subjected to distillation as is to recover fractions boiling between 110. and 400 F. and between 400 and 600 F. A second portion was treated with sodium hydroxide solution in an amount of 50 volume per cent. The sodium hydroxide solution had a strength of 5 B. The second portion, after separation from the caustic solution, was subjected to distillation conditions under comparable conditions to those used for the first portion to obtain fractions boiling between 110 and 400 F. and between 400 and 600 F.

The third portion was treated in accordance with the present invention in that it had added to it an admixture containing oil and sodium sulfonates to which had been added about 40weight per cent sodium hydroxide. Ten volumes of this mixture was added to the naphtha and the naphtha distilled under conditions comparable to those used in the other runs to obtain fractions having similar boiling ranges. The fourth portion was distilled over a mixture of oil and sodium Table Distilled over Washed with mixture of 011, Distilled Treatment None N110? and then petroleum sodium gg ggi iggg over 50 istilled snlfolggisHand Sod. sulfonates Be. NaOIl Boiling range, "F 110-400 400-600 110-400 400-600 110-400 400-600 110400 110-400 110-400 Analysis:

Oxygenated Organic Compounds, weight per cent (expressed as functional de t; h 1s) 93 0 21 o 40 0 co 0. 0 0.87 0.10 0.70 0.00 1.12 CHO (a1de hydes)-.- 0.62 0.15 0.82 0.33 0.00 0.10 0.30 0.30 0.00 COOH (acids) 0.92 0.47 0.00 0.00 0.00 0. 00 0.50 0.30 0.00 000 (esters)... 0.64 3.38 0.39 0.31 0.00 0.00 0.70 1.35 0.00 00 (ketcnes). 1.13' 0.27 1.33 0. 91 0.13 0. 1.10 0.10 0.55

layer and an aqueous layer. -The hydrocarbo It will be apparent from the foregoing data that the fractions boiling between 110 and 400 F. and 400 and 600 F. obtained by distillation without any treatment of the naphtha contained considerable amounts of theseveral oxygenated organic compounds. Treatment of the naphtha prior to distillation with the sodium hydroxide solution served to reduce the content of alcohols,

increase the content of aldehydes, remove substanti-ally the organic acids, and reduce the amount of esters, but resulted in increased amounts of ketones. The fractions obtained by distillation over a mixture of oil and sodium sulfonates and over the B. sodium hydroxide,

respectively, contained appreciable quantities of alcohols, aldehydes, acids, esters, and ketones.

Comparing these four runs with the run in accordance with the present invention, it will be noted that the present invention allows a substantial reduction in the aldehyde, acid, ester, and ketone content of the contaminated naphtha. The lighter fraction obtained in accordance with the present invention had a high content of alcohols but this is no particular problem since the alcohol may be removed by well-known procedures. The ketones especially resist conventional methods of removal and the beneficial aspects of the present invention in this respect should be emphasized. Attention is also directed to the fact that neither the strong sodium hydroxide solutions nor the mixtur of oil and sodium sulfonates were as effective as the mixture of the two employed as the treating reagent in accordance with the present invention.

It is not understood why a mixture of oil, alkali metal sulfonates, and alkali metal hydroxide gives .better results than the components of the mixture taken alone, but it is theorized as one explanation of the beneficial results that, since the alkali metal sulfonates are miscible with the contaminated hydrocarbons containing oxygenated organic compounds in substantially all propor- 5 tions, their principal function is to serve as a carrier for the alkali metal hydroxides. The function of the high boiling lubricating oil fraction is-to fiuidize the mixture and make it available fo contact with the contaminated hydrocarbon fraction allowing substantially complete removal of the deleterious oxygenated organic compounds. It is to be understood, of course, that this explanation of the beneficial aspects of the present invention is given solely for illustration purposes and for 'a better understanding ofthe invention, and it is not to be construed as limiting our invention in any manner whatsoever.

The nature and objects of the present invention, having been fully described and illustrated, what we wish to claim as new and useful and to secure by Letters Patent is:

1. A method for removing oxygenated organic compounds including ketones, "aldehydes and esters from a synthetic crude petroleum containing them in substantial-quantities which comprises subjecting the synthetic crude petroleum containing the oxygenated compounds to distillation in the presence of a treating reagent comprising a hydrocarbon fraction boiling in the lubricating oil boiling range, an alkali metal sulfonate, and an alkali metal hydroxide and recovering a distillate fraction having a boiling point no greater than 600 F. which is substantially free of oxygenated organic compounds.

2. A method for removing oxygenated organic compounds including ketones, aldehydes and esters from a synthetic crude petroleum containing them in substantial quantities which comprises, forming a mixture of thesynthetic crude petroleum containing the oxygenated organic compounds and a treating reagent comprising a hydrocarbon fraction boiling in the lubricating oil boiling range, an alkali metal sulfonate, and an-alkali metal hydroxide, subjecting the admixture to conditions of distillation at an elevated temperature, and recovering a fraction boiling in the gasoline boiling range which is substantially free of oxygenated organic compounds.

3. A method in accordance with-claim 2 in which the hydrocarbon fraction is admixed with sulfonate, and the alkali metal hydroxide is sodium hydroxide. I

5. A method for removing oxygenated organic compounds including ketones, aldehydes and esters from a hydrocarbon fraction obtained from the synthesis of carbon monoxide and hydrogen over an iron catalyst which comprises admixing the hydrocarbon fraction from the the synthesis of &110011 monoxide and hydrogen over an iron catalyst with a treating reagent comprising a hydrocarbon fraction boiling in the lubricating oil boiling range, an alkali metal sulfonate, and an alkali metal hydroxide, subjecting the admixture to distillation conditions and recovering from said distillation a fraction boiling in the gasoline boiling range substantially free of oxygenated organic compounds.

6. A method in accordance with claim in which the hydrocarbon fraction is admixed with an amount of the treating reagent in the range from about 5 to about 30 volume per cent.

7. A method in accordance with claim 5 in which the fraction boiling in the lubricating oil boiling range is a solvent extract of a lubricating oil fraction, the alkali metal sulfonate is sodium sulfonate, and. the alkali metal hydroxide is sodium hydroxide.

8. A method for removing oxygenated organic compounds including ketones, aldehydes and esters from the hydrocarbon fraction containing them which comprises subjecting the hydrocarbon fraction containing the oxygenated organic compounds to distillation in the presence of "a treating reagent comprising 75% to 90% of a hydrocarbon fraction boiling in the lubricating oil boiling range, 10% to of an alkali metal sulfonate to which has becn added an amount of an alkali metal hydroxide sufiicient to provide an amount of alkali metal hydroxide in said treating reagent in the range between 10% and BOYD N. HILL. EDWARD F. WADLEY.

REFERENCES CITED UNITED STATES PATENTS Name Date Petrofi July 17, 1917 Number 

1. A METHOD FOR REMOVING OXYGENATED ORGANIC COMPOUNDS INCLUDING KETONES, ALDEHYDES AND ESTERS FROM A SYNTHETIC CRUDE PETROLEUM CONTAINING THEM IN SUBSTANTIAL QUANTITIES WHICH COMPRISES SUBJECTING THE SYNTHETIC CRUDE PETROLEUM CONTAINING THE OXYGENATED COMPOUNDS TO DISTILLATION IN THE PRESENCE OF AS TREATING REAGENT COMPRISING A HYDROCARBON FRACTION BOILING IN THE LUBRICATING OIL BOILING RANGE, AN ALKALI METAL SULFONATE, AND AN ALAKLI METAL HYDROXIDE AND RECOVERING A DISTILLATE FRACTION HAVING A BOILING POINT NO GREATER THAN 600* F . WHICH IS SUBSTANTIALLY FREE OF OXYGENATED ORGANIC COMPOUNDS. 